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Title:A Kinetic and Thermodynamic Study of Exciplex Fluorescence Quenching by Ion Pairs
Author(s):Hartley, Rolfe John
Department / Program:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Subject(s):Chemistry, Analytical
Abstract:Tetraalkylammonium salts are shown to quench the fluorescence of the pyrene-N,N-dimethylaniline exciplex in solvents of low dielectric constant. Linear Stern-Volmer plots are obtained for quenching of both lifetime and intensity in dioxane. However, mechanistic complications are implied by intercepts exceeding unity and by the unequal slopes of these plots. Qualitatively similar behavior is observed when the solvents and electrolytes are varied. Historic conductivity data indicate that the quenching species Q in dioxane are aggregates of electrolyte ions, probably ion pairs or quadrapoles. A proposed kinetic model is both qualitatively consistent with the experimental observations and quantitatively self-consistent. An emitting complex formed at a diffusion-controlled rate by an encounter between Q and an exciplex is postulated. The emitting complex is apparently quenched by subsequent encounters with additional Q at rates considerably below the encounter-limited value.
Issue Date:1986
Description:146 p.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1986.
Other Identifier(s):(UMI)AAI8623313
Date Available in IDEALS:2014-12-15
Date Deposited:1986

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